DD200572A5 - ADDITIVE COMBINATIONS - Google Patents

Abstract

The invention relates to an additive combination for the addition to Heizoelen. The aim of the invention is to prevent paraffin agglomeration even at long storage times of the oil at low temperatures and to control and moderate the crystal size. According to the invention, the novel additive combinations for heating oil distillates, the following classes (A), (B) and (C): (A) a distillate flowability improving composition, (B) a high molecular weight hydrocarbon polymer of average relative molecular mass over 10 high 3 or a version derived therefrom, and (C) a polar oelloic compound other than (A) and (B).

Description

C 1OG / 226 870/2 - - / - 58 47.8 / 18

Additive combination Field of application of the invention

The invention relates to an additive combination "It is used as an additive to fuel oils"

Characteristic of the known technical solutions

Additive systems for the treatment of heating oil distillates to improve the flow of paraffin-contaminated fuels through pipelines and filters in cold weather are already known, as the following patents show.

British Patents 900,202 and 1,263,115 relate to the use of low molecular weight ethylene copolymers and unsaturated esters such as, in particular, vinyl acetate, while British Patent 1,374,051 (UK patent) relates to the use of an additive system. which both increases the starting temperature of paraffin crystallization and limits the size of the paraffin crystals. The use of low molecular weight ethylene copolymers as well as other olefins as pour point depressants for heating oil distillates is described in British Patent Nos. 848,777, 993,744 and 1,068,000 as well as U.S. Patent 3,679,380. Various other polymer specialty types as additives for fuel oil distillates are disclosed in U.S. Patent Nos. 3,374,073, 3,499,741, 3,507,636, 3,524,732, 3,608,231 and 3,681,302.

In addition, it has been proposed to use combinations of additives to further improve the flow and pour point properties of heating oil distillates. For example, US Pat. No. 3,666! 541 on the insert

f> in jftnj. η f. e η η

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of combinations of additives of the ethylene / unsaturated ester copolymer type and of the low molecular weight ethylene-propylene copolymer type of GB-PS 993 744, in which the copolymers contain small amounts of propylene.

US Pat. No. 3,658,493 refers to various nitrogen salts and acid amides, such as amides of mono- and dicarboxylic acids, phenols or sulfonic acids, in combination with ethylene homo or copolymer pour point depressants for medium distilled oils.

US Pat. No. 3,982,909 discloses nitrogen compounds such as amides, diamides and ammonium salts of monoamides or monosters of dicarboxylic acids - alone or in combination with petroleum-derived microcrystalline paraffin and / or a pour point depressant (especially a polymeric pour point depressant with ethylene backbone) Paraffin crystal modifiers and cold flow improvers for medium-distilled oils, in particular diesel fuel ·

US Pat. Nos. 3,444,082 and 3,946,093 teach the use of various amides and amine salts of alkenyl succinic anhydride in combination with ethylene copolymer pour point depressants in H.sub.2 oil distillates.

The above-described additives are basically for lowering the flow point of fuel oil distillates by preventing the oil gelation due to paraffin crystal formation and / or improving the filter flowability of paraffinic oil by reducing the paraffin crystal sizes. Despite all the importance of achieving these effects, it is desirable to reduce the crystal size even more, as is another problem in fluidity-improved oils, that the paraffin crystals formed upon storage of the oil under cold weather conditions tend to agglomerate and. thus to raise distribution difficulties.

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Due to the large volume of oil in storage containers, the oil temperature drops only slowly, even if the ambient temperature drops considerably below the cloud point of the oil - the temperature at which the paraffin begins to crystallize and become visible starts - lies. If the winter is unusually cold and long-lasting, so the oil is stored for a long time in very cold weather, then the oil temperature may fall even below the cloud point even in large commercial tank facilities. This may then be in the form of paraffin agglomeration, which is increasingly increasing as the higher density paraffin concentrated in the lower part of the tank

Object of the invention

The aim of the invention is to provide new additive combinations which prevent paraffin agglomeration even at long storage times of the oil at low temperatures and allow a better control of the crystal size «

Explanation of the essence of the invention

The invention has for its object to find suitable components that added in combination the fuel oils, achieve the desired effect.

According to the invention, the novel additive combinations comprise substances of classes (A), (B) and (G) described below:

(A) a distillate flow improving composition,

(B) a high molecular weight hydrocarbon polymer having

average molecular weight greater than 1Cp (preferably g derived version and

as 1Cp (preferably greater than 1Cr) or its

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(G) a polar oil-soluble compound other than (A) and (B) of the formula RX described below.

According to our findings, these combinations therefore also such with the aforementioned additives are particularly suitable for limiting the growth and agglomeration of wax precipitations for fuel oil distillates boiling point range of 120-500 ⁰ C and specifically in the boiling point range between 16O and 400 G. The present invention comprises Combinations equipped heating oil distillates.

The total additive content in the fuel oil is between 0.001 and 1.0 weight percent, suitable range is 0.001 to 0.5 weight percent (eg, 0.005 to 0.2), more suitably 0.01 to 0.2 weight percent, most preferably a range of 0.005 to 0.05 weight percent (eg, 0.02 to 0.1) appears. This ^z usatzstoffgehalt may consist of a combination of (A), (B) and (G) in a mixing ratio of 0.1 to 10 parts by weight of the three components are to each other. We prefer a combination of one part by weight of fluidity improver (A) 0.1 to 10 (preferably 0.2 to 2) parts by weight of the hydrocarbon polymer (B) and 0.1 to 10 (preferably 0.2 to 1) parts by weight of the polar oil-soluble compound (C).

For ease of handling, the additives are generally supplied as concentrates added with 10 to 90 weight percent (preferably 30 to 80 weight percent) of a hydrocarbon diluent. The present invention also relates to such concentrates.

The flowability improver (A) used in the additive combinations of the present invention is a wax crystal growth stopper and may additionally have a

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Crystallization nucleator (nucleator) for the paraffin »crystals, as defined in GB-PS 1 374 051. Such growth arrestor and nucleators are preferably those ethylene polymers as described in the industry as the wax crystal modifiers 'are beispielsweiseFließpunktserniedriger and cold flow improver for fuel oil distillates known _e possess These polymers by hydrocarbon or oxy-hydrocarbon side chains, by alicyclic or heterocyclic structures, or by' Chlorine atoms segmented backbone · These may be ethylene homopolymers as produced by free radical initiated polymerization and some branching resulting therefrom. More often, it will be copolymers of about 3 to 40 (preferably 4 to 40) 20) molar proportions of ethylene per molar fraction of a second, defined below, ethylenically unsaturated monomer, the latter may be a simple monomer or a mixture of monomers in any proportion. The polymers will generally have an average molecular weight in the range of 500 to 50,000 (e.g., 500 to 10,000, but preferably 1,000 to 6,000) as measured by vapor pressure osmometry (VPO).

The unsaturated monomers that can be copolymerized with ethylene include unsaturated mono- and diesters of the general formula

R ₁ H

I i

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wherein R is hydrogen or methyl; Rp represents an -OOCR ^ group in which R. is hydrogen or a single or branched chain alkyl group of length CL to Cq; or Rp is a -COC-R * group, where R * does not occur as hydrogen, but otherwise corresponds to the description just given; Finally, R _{1 represents} hydrogen or a -COOR. Group as described above. The monomer when R ₁ and R 0 are hydrogen and R _{2 is} COCR * includes CL to C ₂ -Q vinyl alcohol esters (most commonly C j to C..Q -), Monokarbonsäure and in this case preferably Op- to Cc monocarboxylic acid. Examples of such esters include vinyl acetate, vinyl isobutyrate, vinyl myristate and vinyl palmitate, with vinyl acetate being the preferred ester. When H _{2 is} -COOR * and R _{1 is} hydrogen, then these esters include methyl acrylate, isobutyl acrylate, methyl methacrylate, lauryl acrylate, C. v oxo alcohol esters of methacrylic acid, etc. Examples of monomers in which R _{1 is} hydrogen and R ₂ and RyCOOR. Groups include mono- and di-esters of unsaturated dicarboxylic acids such as mono-coco-oxo-fumarate, di-C ₁ 3-0x0 fumarate, di-isopropyl maleate, Di-lauryl fumarate and ethyl methyl fumarate. In all of the monoesters, the remaining carboxyl group is reacted with an amine to give either an amine salt or the amide of a hemiester.

Another class of monomers that can be copolymerized with ethylene, encloses the C, - to C ~ _o - (preferably C -, - C ₁ Q) alpha-mono-olefins which are branched as well as can be straight-chain such as / Propylene, isobutene, n-octene-1, n-decene-1, dodezene-1, etc. »

Still other monomers include vinyl chloride, although ultimately the same result is achieved by chlorinating polyethylene, e.g. B. can be achieved up to a chlorine content of about 35 weight percent.

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The distillate fluidity improvers also include those based on hydrogenated polybutadienes which, like the products of US Pat. No. 3,600,311, are formed mainly by 1,4-addition and 1,2-addition.

The preferred ethylene copolymers are ethylene-vinyl ester copolymers and in particular vinyl acetate copolymers. The latter can be prepared at high pressure in the presence or absence of a solvent. If the copolymerization in solution, then the solvent and 5 to 50 weight percent of the total amount of monomer (without ethylene) added are charged into a stainless steel pressure vessel equipped with stirrer and heat exchanger. The pressure vessel is then at the desired reaction temperature -. B. 70 to 200 ⁰ C - brought while simultaneously in the autoclave with ethylene, the pressure to the desired amount -. 49 to 1758 at (700 to 25,000 psig) but usually 63 to 492 at (900 to 7,000 psig). The initiator, generally diluted in the polymerization solvent (or, in the case of solids), is injected during the polymerization; At the same time in the reaction time additional amounts of the monomer charge (but no ethylene) - ie z. As the vinyl esters - continuously or at least periodically pumped into the boiler. If ethylene is consumed in the polymerization reaction, additional ethylene is likewise to be fed in via a pressure regulator during this reaction time in order to maintain the desired reaction pressure with great accuracy. The temperature of the copolymerization is kept substantially constant with the aid of the heat exchanger. After completion of the reaction - usually a total reaction time of

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1/4 to 10 h - the liquid phase is removed from the reactor. The solvent and other volatiles of the reaction mixture are desorbed leaving the copolymer as a residue. To facilitate handling and mixing, the polymer is generally dissolved in a mineral oil, preferably an aromatic solvent such as high aromatic gasoline, to form a concentrate which usually contains from 10 to 60 percent by weight of the copolymer.

The initiator is selected from a class of compounds which undergo cleavage of the extending radicals at elevated temperatures - such as peroxide or azo type initiators including the acyl peroxides from Gp to Cg (branched or unbranched), the carboxylic acids as well other conventional activators. Specific examples of such initiators include dibenzoyl peroxide, di-tertiary-butyl peroxide, t-butyl perbenzoate, t-butyl peroctoate, t-butyl hydrogen peroxide, alpha, alpha ', azo-diisobutyronitrile, dilauroyl peroxide, etc. The choice of peroxide is primarily determined by to be used Poylmerisationsbedingungen, the desired polymer structure and the effectiveness of the initiator. Preferred initiators are t-butyl peroctanoate, dilauroyl peroxide and di-t-butyl.

The high molecular weight oil-soluble hydrocarbon (B), preferably an olefin copolymer, should, after examination by gel permeation chromatography or (better) membrane osmometry, have an average molecular weight of 10 x 10-10, and more preferably 20,000 to 250,000, more preferably 20,000 to 150,000 or, most preferably, 50,000 to 150,000 and 10,000 to 50, respectively. Examples of suitable hydrocarbon polymers include homopolymers and copolymers of two or more monomers of C ₂ to Co _n , ie, for example,

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Cg to Gg olefins including both alpha-olefins and internal olefins, which may be straight or branched, aliphatic, aromatic, alkylaromatic, cycloaliphatic, etc. Often they consist of ethylene with Co to CoQ olefins; in particular preferred are ethylene and propylene copolymers and polymers of other olefins such as propylene and butene and also the proven polyisobutylenes. In addition, homopolymers and copolymers of Cg and higher alpha olefins can be used to advantage.

Such hydrocarbon polymers also include olefin polymers such as tactic polypropylene, hydrogenated polymers and copolymers, and styrene terpolymers, for example, with isoprene and / or butadiene. The polymer may be in terms of its molecular weight z. G., By mastication, extrusion, oxidation or thermal degradation, and it can be oxidized and contain oxygen. Also included are derived polymers such as post-polymerized ethylene-propylene interpolyraers with an active monomer such as maleic anhydride, which may be further characterized by an alcohol or an amine such as e.g. For example, an alkylene polyamine or a hydroxyamine (see, for example, U.S. Patent 4,089,794, 4,160,739 * 4,137,185) can be reacted. "Ultimately, ethylene and propylene copolymers that react with nitrogen compounds are also included were brought or polymerized as described in US-PS 4,068,056; 4,068,058; 4,146,489. Ultimately, the oil-soluble polymer can also be a viscosity index improver »

The preferred hydrocarbon polymers are ethylene copolymers containing from 15 to 90 weight percent ethylene (preferably from 30 to 80 weight percent ethylene) and from 10 to 85 weight percent (preferably from 20 to 70 weight percent ethylene).

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% or more) of one or more CL to Cpo- (preferably Co to C ₁ Q, even better Gy to Cg) alpha olefins. More preferably, though not necessarily, these copolymers have a degree of crystallinity as determined by X-ray and differential screens Calorimetry - of less than 25 weight percent. Ethylene and. Propylene copolymers are most preferred. Other than propylene for copolymer formation or in combination with ethylene and propylene to form a terpolymer, tetra polymer, etc. Alpha-olefins include 1-butene, 1-pentene, 1-hexene, 1 -Hepten, 1-Okten, 1-Nonen, 1-Dezenusw .; Also included are branched-chain alpha-olefins such as 4-methylene-1-pentene, 4-methyl-1-hexene, 5-methylpentene-1, 4,4-dimethyl-1-pentene, 6-methylheptene-1, etc., and the like mixtures

Also useful are kthylene terpolymers, tetrapolymers, etc., the aforementioned Co to Cgg alpha olefin, a non-conjugated diolefin or mixtures of such diolefins. The amount of non-conjugated diolefin - as measured by the total amount of ethylene and alpha-olefin present, varies from 0.5 to 20 mole- $, preferably from about 1 to about 7 mole-%.

Representative examples of nonconjugated dienes that can be used as the third monomer in the terpolymer are

a) straight-chain acyclic dienes such as 1,4-hexadiene; 1,5-heptadiene, 1,6-octadiene,

b) branched-chain acyclic dienes such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene and the mixed monomers of dihydro-myrcene and dihydro-zymol,

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c) alicyclic single ring dienes such as 1,4-cyclohexadiene; 1,5-cyclooctadiene-1,5-cyclododecadiene, 4-vinylcyclohexene; 1-allyl, 4-isopropylidene-cyclohexane; 3-allyl-cyclopentene-4-allyl-cyclohexene and 1-isopropenyl-4- (4-butenyl) cyclohexane,

d) multi-ring acyclic dienes such as 4 ₉ 4'-dicyclopentenyl and 4 '4'-dicyclohexenyl dienes,

e) Acyclic condensed and bridged multi-ring dienes

such as tetrahydroindene; Methyl tetrahydroindene} dicyclopentadiene; Bizyklo (2.2.1) hepta 2,5-diene; Alkyl, alkenyl, alkylidene, cycloalkenyl and cycloalkylideneborbonene such as ethylnorbornene; "Methylene-6-methyl-2-norbornene, 5"; 5-methylene-6,6-dichloro-2-norbornene 5-propenyl-2-norbornene; 5- (3-cyclopentenyl) -2-norbornene and 5-cyclohexylidene-2-norbornene; Norbornadiene etc.

Among the compounds mentioned above, particularly suitable di-olefins are: cyclopentadiene, 2-methylene-5-norbornene, nonconjugated hexadiene or any other alicyclic or aliphatic non-conjugated diolefin having 6 to 15 carbon atoms per molecule such as 2-methyl or ethyl norbornadiene, 2- _i- 4-diraethyl-2-octadiene, 3- (2-methyl-1-propene) cyclopentene, ethylidene norbornene, etc.

The conventional polymers, tetrapolymers, etc., used in connection with the present invention preferably contain at least 30 mol%, but preferably not more than 85 mol%, of ethylene; from about 15 to about 70 mole% of a higher alpha-olefin or mixture thereof, preferably propylene, and from 1 to 20 mole%, preferably from 1 to 15 mole% of a non-conjugated diene or mixture thereof.

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Especially preferred are polymers of about 40 to 70 mol% of ethylene, from 20 to 58 mol% of a higher monoolefin and 20 to 10 mol -%, diene _e is on a weight basis constitute the diene is generally at least 2 or 3 weight percent of the total terpolymer »

Polyisobutylenes can be readily prepared in a known manner in accordance with US Pat. No. 2,084,501 by subjecting the isoolefin, Z ₀ B _e isobutylene, using a suitable Friedel-Crafts catalyst such as B ₉ borofluoride, aluminum chloride, etc., at temperatures considerably below 0 ⁰ C - is polymerized "such polyisobutylenes can also U.S. Patent 2,543,095 be polymerized with a higher straight chain alpha-olefin has from 6 to 20 carbon atoms also according to where the polymer mentioned therein about 75 to 99 percent by volume - about -40 ⁰ C. Contains isobutylene and about 1 to 25 volume percent of a higher normal alpha olefin of 6 to 20 carbon atoms «

Such ethylene copolyesters - this term includes terpolymers, tetrapolymers, etc., - can be prepared using the well-known Ziegler-Natta catalyst compositions as described in GB-PS 1,397,994. "

Such a polymerization to produce the ethylene copolymers can be accomplished by adding 0.1 to 15 »eg. B, 5 parts of ethylene, 0.05 to 10 - ie z. B. 2.5 parts - said higher alpha-olefin (essentially propylene) and 10 to 10,000 parts of hydrogen per 1 000 000 parts of ethylene in 100 parts of a .reaktionsschwachen liquid solvent are introduced, the latter a) 0.0017 bis 0.017 (eg, 0.0086) parts of a major transition metal catalyst (z ₉ B ₈ , VOCl 2), and b) 0.0084 to 0.084 (eg, 0.042) parts of a Ka cocatalyst - z "B, (CnH , -) «JÜ ^ Clo - must contain«

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All quantities are to be understood as parts by weight. The polymerization takes place at a temperature of about 25 ⁰ C and a pressure of 4.2 atmospheres (6o psig) for a sufficient for the execution of the optimum conversion time, so about 15 to 30 min instead of "

Other suitable hydrocarbon polymers can be prepared from styrene or substituted styrenes such as alkylated or halogenated styrene. The alkyl group in the alkylated styrene, as a substituent on the aromatic ring or on an alpha carbon atom, can be from 1 to about 20 carbon atoms, but preferably from 1 to 6 Contain carbon atoms. These styrene-type monomers may be copolymerized with suitable conjugated diene monomers including butadiene and alkyl-substituted butadiene, etc., wherein the alkyl substituent contains from 1 to about 6 carbon atoms. Thus, in addition to butadiene, isoprene, piperylene, and 2,3- Dimethyl butadiene can be used as the diene monomer. Two or more different Styren ™ type monomers as well as two or more different conjugated diene monomers can be polymerized to form interpolymers. Still other useful polymers are derived without styrenes and only aliphatic and conjugated dienes usually having from 4 to 6 carbon atoms; most useful here is butadiene. Examples include homopolymers of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-dimethyl-butadiene and copolymers of at least two of these conjugated dienes and finally copolymers of the latter with styrene, these homopolymers and copolymers have been hydrogenated , The aforementioned polymers with pronounced unsaturation are advantageously fully hydrogenated to the total olefinic unsaturation

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permanently eliminated, although in certain situations, only a partial saturation of the aromatic unsaturation is made. These interpolymers are produced by conventional polymerization techniques, ie, by the formation of interpolymers with a controlled type of steric arrangement of the polymerized monomers - ζ » B. random arrangement, block, conical arrangement, etc. The hydrogenation of the interpolymer proceeds using conventional hydration processes«

A separate subclass of class B are those hydrocarbon polymers described above, to which polar groups have been added, for example, by grafting maleic anhydride (as a consequence of amination) or by phosphorus sulfurization. Likewise, it may be sulfonated, phosphorated, oxidized, halogenated (Β _{Φ Φ} chlorinated or brominated), epoxidized, chlorosulfonated, hydroxylated or with other monomers such as vinylpyridine, etc. added hydrocarbon polymers.

The polar compound (G) is different from (A) and (B), basically monomeric, and may be ionic or nonionic. The compound is said to inhibit the agglomeration of paraffin crystals sustained by the fact that the compound is adsorbed by their hydrocarbon fractions to the crystal planes.

Suitable polar compounds of the class "G" may be both nonionic and ionic; in the case of ionic compounds, they may be combinations of mono- or polyfunctional anions and cations «

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Monofunctional oil-soluble ionic and nonionic compounds can be represented by the formula RcX, salts can be represented by the formula HcX ZRg, where Rc corresponds to an oil-solubilizing group and X to the polar group,

R _c is one or more substituted or nichtsub o

be substituted, saturated or unsaturated hydrocarbon groups; R 1 can be aliphatic, cycloaliphatic or aromatic, preferably it is an alkyl, alkaryl or alkenyl; if possible, R, - should be saturated. Rj- should advantageously contain a total of 8 to 150 carbon atoms.

If the compound RX is nonionic, then we prefer a carbon content of RX between 14 and 60, more favorably 16 to 40 carbon atoms. If RcX is an anion then Rc should contain from 8 to 150 carbon atoms, more preferably 12 to 50, most preferably 14 to 40 carbon atoms. In particular, we emphasize the fact that the alkyl groups contain 1 to 35, more preferably 12 to 30, carbon atoms. Rc is comprised of alkyl groups, they should be straight-chain _e In the alternative case _R1 may - be an alkyl oxy Ii erte chain.

Examples of suitable polar groups X include the carboxylate C00 ", the sulfonate SOt group, the sulfate OSO ^ group, the phosphate OgPOÖ group, the phenolate PhO ~ group and the borate OpBO" group. Thus, our preferred anions include RyCOO "*, RySOO, RyOSOOi (RyO) ₂ PO ₂ , RyPhO", and (RyO) ₂ BO ", where Ry represents the oil solubilizing hydrocarbon group, the total carbon atom content of Ry being in the previously described limits for Rc.

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If the anion is a sulfonate, then we prefer to use an alkaryl sulfonate, which may be one of the well-known neutral or basic sulfonates. If the anion is a phenolate, then we prefer one of alkylphenol or bridged phenols, including those of the general formula

O O

<Vn

derived version; in the latter, M represents a linking group of one or more (eg, 1 to 4) carbon or sulfur atoms, Ry corresponds to the description given above. Again, the phenolate used may be one of the well-known neutral or basic compounds.

Alternatively, when the anion is a borate, sulfate or phosphate, then R 1 can be alkolylated chains. Examples of such compounds in the case of sulfates include the

(R ₈ - (0CH ₂ 0H ₂ ) _n - 0) - group and in the case of phosphates and borates the

(R ₈ - (OGH ₂ CH ₂ ) _n --O) ₂ - group,

wherein the total carbon atom content of the R ₈ components corresponds to that mentioned above for R, -.

The cation for these salts is preferably a mono-, di-, tri- or tetra-alkyl ammonium or phosphonium ion of the formula

T RgZH ⁺ ; (Rg) ₂ HZ ₂ -; (Rg) ₃ ZH ⁺ ; (Rg) ₄ Z ⁺ ,

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where R 1 is a hydrocarbyl and preferably an alkyl group. If the cation contains more than one of these groups then they may be the same or different and Z is then nitrogen or phosphorus. Rg should contain 4 to 30, better still 14 to 20 carbon atoms; it is also desirable that Rg be composed of straight-chain alkyl groups,

Examples of suitable alkyl groups include methyl, ethyl, propyl, n-octyl, n-dodecyl, n-tridezyl, C 1 -oxo, coconut, hydrogenated tallow, behenyl, lauryl.

The Rg group may be substituted - for example by hydroxy or amino groups (such as in the polyamine). In another embodiment, the hydrocarbyl group of the cation may contribute the property of oil solubilization; This is the case, for example, with the salts of fatty amines, such as hydrogenated tallowamine.

Derivatives of alkyl-substituted dicarboxylic acids or their anhydrides can also be used as a polar compound. So z. B. succinic acid derivatives of the general formula

wherein at least one of the Rg or R-Q constituents represents a long chain carbon atoms (eg, from 10 to 120, but preferably from 12 to 100) of the alkyl or alkenyl group, eg, polyisobutylene or polypropylene

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The other Rq or R- _Q ingredient may be similar or even hydrogen. P and Q may be the same or different from each other, they may be hydroxy or alkoxy groups, together they may also form an anhydride ring ·

In a less preferable alternative, the cation can be metallic. If possible, however, it should be an alkali metal such as sodium or potassium or an alkaline earth metal such as barium, calcium or magnesium.

Although the above-described ionic type compounds are the polar oil-soluble ones we prefer. Nonetheless, we have found that polar nonionic compounds are also suitable. For example, primary amines of the formula R 1 -NH ₂ O-> secondary amines (R--) ₂ NH and primary alcohols R 1 -0 H can be used provided that they are oil-soluble. To achieve the latter, R-1 should optionally contain at least 8 carbon atoms and, moreover, the carbon content should be specified in the manner indicated above for Rr.

In particular, nitrogen compounds are suitable polar substances for keeping the individual paraffin crystals apart by inhibiting paraffin crystal agglomeration. They are thus the component (C) of the additive combinations preferred by us. Examples of suitable compounds include oil-soluble ammonium salts, amine salts and / or imides, which are generally formed by reaction of at least one molar portion of an amine with a molar fraction of a hydrocarboxylic acid or its anhydrides. The Hydrokarbylsäure must have 1 to 4 carboxylic acid groups.

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In the case of polycarboxylic acids or their anhydrides, all acid groups can be converted to amino salts or amides; Likewise, some of the acid groups can be esterified by reaction with hydrocarbyl alcohols, or remain unchanged. Examples of suitable amides are those of succinic acid, as set forth in British Pat. No. 1 HO 771.

The hydrocarbyl groups of the nitrogen compounds described above may be straight or branched chain, saturated or unsaturated, aliphatic, cycloaliphatic, an aryl or alkaryl. Bs are long chains of z _e B, CLg to CLq, but preferably Cj * to C24. Nonetheless, some short chains (e.g., Cj to C ^) may be included, provided that the total number of carbon atoms in the compound is sufficient to the required solubility in the heating oil distillate. Generally, a total of 30 to 300 (eg, 36 to 16O) carbon atoms will suffice to provide oil solubility, although the number of carbon atoms required will vary depending on the degree of polarity of the compound. If possible, the compound will also contain at least one straight-chain alkyl segment of 8 to 40, but preferably 12 to 30 carbon atoms. This straight-chain alkyl segment may be present in one or more of the amines or ammonium ions; it can be present in the acids or in the alcohol (if an ester group is also present). Necessarily, at least one ammonium salt, amino salt or amide linkage must be present in the molecule.

The hydrocarbyl groups may contain other groups or atoms such as hydroxy groups, carbonyl groups, ester groups or oxygen, sulfur or chlorine atoms.

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The amines that can be reacted with the carboxylic acids include primary, secondary, tertiary, quaternary, but preferably secondary, amines. If amides are to be prepared, then the primary or secondary amines are used.

Examples of primary amines include n-dodecylamine, n-r-tridezylamine, G-ooxoamine, cocoamine, tallowamine, and behenylamine. Examples of secondary amines include methyllaurylamine, dodecyl-octylamine, cocoamethylamine, tallow-methylamine, methyl-n-octylamine, methyl-n-dodecylamine, methyl-behenylamine and di-hydrogenated tallowamine.

As examples of tertiary amines are coco-diethylamine, cyclohexa-diethylamine, coco-dimethylamine, methyl-IertyI-stearylamine, etc., methyl-ethyl-cocoamine, methyl-cetylstearylamine, etc. mentioned.

Finally, examples of quaternary ammonium cations or salts include dimethyldiethylammonium and dimethyldistearylammonium chloride.

In addition, it is also possible to use amine mixtures, as are many amines derived from natural products. So are those derived from coconut oil cocoamines mixtures of primary amines with straight chain alkyl groups in the range from Cg to C ^ g ₄ Another example is the tallow acids derived from hydrogenated tallow amine. This amine contains a mixture of gjeradkettigen alkyl groups having 14 to 18 carbon atoms. Hydrogenated tallow amine is especially preferred.

The examples of carboxylic acids or carboxylic acid anhydrides include formic acid, acetic acid, hexanoic acid, lauric acid,

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Myristic acid, plamitic acid, hydroxy stearic acid, behenic acid, naphthenic acid, salicylic acid, linoleic acid, dilinoleic acid, trilinoleic acid, maleic acid, maleic anhydride, fumaric acid, succinic acid, succinic anhydride, the already described alkenyl succinic anhydrides, adipic acid, glutaric acid, sebacic acid, lactic acid, malic acid, malonic acid, citric acid, phthalic acids (Ortho -, meta- or para-), ζ »Β. Terephthalic acid, phthalic anhydride, citric acid, gluconic acid, tartaric acid, 9,10-dihydroxy-stearic acid and cyclohexane-1,2-dicarboxylic acid »

Specific examples of alcohols that can also be reacted with the acids include 1-tetradecanol, G, .-, to Cg oxo alcohols (prepared from a mixture of cracked paraffin olefins), 1-hexadecanol, 1-octadecanol, behenyl , 1,2-dihydroxyoctadecane and 1,10-dihydroxydecane.

The amides may be recovered in a conventional manner by heating a primary or secondary amine with acid or acid anhydride. In a similar conventional manner, the ester is prepared by heating the alcohol and polycarboxylic acid to partial esterification of the acid or anhydride, leaving one or more carbon groups for reaction with the amine to form the amide or amino salt.

The alkyl ammonium salts are also prepared conventionally by simply mixing the amine (or ammonium hydroxide) with the acid or acid anhydride, or the partial ester of a polycarboxylic acid or partial amide of a polycarboxylic acid, by subjecting the mixture, in general, under moderate heating (z _e, 60 to 80 ⁰ C) is stirred. Particular preference is given to nitrogen compounds of the abovementioned type which are derived from dicarboxylic acids

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Mixed aminosalt / amides are most preferred; they are prepared by heating maleic anhydride, alkenyl succinic anhydride or phthalic acid or phthalic anhydride with a secondary amine, preferably hydrogenated tallow amine at a moderate temperature (ζ. Β »60 ⁰ C).

The addition of (G) reduces the size of the paraffin crystals, which in turn can reduce the paraffin settling rate of those heating oils containing only the distillate flowability improvers »

We believe that the presence of such polar compounds is effective under conventional fuel oil storage conditions; This is especially true if the fuel is stored for a long time at low temperatures and the storage temperature is reduced very slowly (eg ₉ ° C. to about 0.3 ° C./h). "

The fuel distillates, in which the additive combinations of the present invention are particularly useful, have their boiling range (z. B. 160-400 ⁰ C) is generally from 120 to 500 ⁰ G. The fuels may be atmospheric distillate or a vacuum distillate, a cracked gas oil or a mixture in any proportion of straight distilled or thermally and / or catalytically cracked distillates. "The most common petroleum distillates are kerosene, jet fuels, Diesel oils and heating oils. The fuel oil may be either a directly distilled or a cracked (cracked) gas oil, or a combination of both. The low flow fluidity problem alleviated by using the additive combination of the present invention is most prevalent in diesel and heating oils.

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However, there is a tendency to increase the final boiling point (PBP) of the distillates in order to maximize fuel yield. However, these fuels contain longer chain paraffins and therefore generally have higher cloud points. This, in turn, increases the problems encountered in the treatment of these fuels under refrigeration conditions and increases the need for the use of flowability improving additives.

It has been found that the additive combination of the present invention is particularly suitable for such fuels.

The term "oil-soluble" imitating used meaning that the additive is soluble in ambient temperature in the fuel that z. B. at least 0.1% by mass of the additive in the fuel dissolved at 25 ⁰ C, although at least a portion of the additive exits the solution near the cloud point to modify the forming paraffin crystals.

embodiment

With regard to the following examples, the invention is illustrated but not limited in any way.

The distillate flow improver A1 used in these examples was a concentrate in an aromatic diluent of about 50% by weight of a mixture of two ethylene-vinyl acetate copolymers of different oil solubilities, so that, in accordance with the teachings of British Patent 1,374 051 - one polymer acted primarily as wax crystal growth stopper and the other polymer as nucleator. Especially are the two

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Polymers in a ratio of about 75% by mass of growth stopper and about 25 Maase-% nucleator before. The wax crystal growth stopper is composed of ethylene and about 38% by weight of vinyl acetate and has an average molecular weight of about 1,800 (vapor pressure osmometry). It is identified in the aforementioned GB-PS 1 374 051 as copolymer B in Example 1 (column 8, lines 25 to 35). The nucleator consists of ethylene and about 16% by weight vinyl acetate and has an average molecular weight of about 3,000 (vapor pressure osmometry). Br is identified in the cited GR-PS 1,374,051 as copolymer H (see Table 1, columns 7 to 8). As Destillatflußverbesserer A2 acted the growth stopper component of the self-employed concentrate A1.

The hydrocarbon polymer B1, useful as a viscosity index (VI) improver of lubricating oil, consisted of an average molecular weight ethylene-propylene copolymer of about 35,000 to 40,000 (as measured by membrane osmometry) containing 44% by mass of substantially linear ethylene and was produced with the help of Ziegler-Natta catalysts »

As polar compounds were used:

C1: A Haib amide / half-alkyl ammonium salt obtained by reacting two moles of dihydrogenated TaIgamine with one mole of phthalic anhydride

G2s The diamide generated by dehydrogenation of C1.

03: Zi-tronensäuretriamid, which was formed by dehydration of the reaction product of 3 moles of dihydrogenated tallowamine and one mole of citric acid.

The fuels and fuels in which the additives were tested are described in the following table *

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Fuel 1 -3 2 3 4 Cloud point, ⁰ G (measured by ASTM D-2500) -6 0 0 -12 Paraffin appearance, ⁰ C (see ASTM D-3117; 180 -2 -2 Distillation, ⁰ G (ASTM D-86): boiling starting point, ° C 170 178 200 20 % boiling point 238 90 % boiling point 365 342 Boiling end point -5 372 365 346 GPPP, ⁰ G (untreated) -1 -2

The initial reaction of the oil to the additives was measured by the Cold Filter Clogging Point Test (CPPPT). A detailed description of this test method is given in "Journal of the Institute of Petroleum", Vol. 52, No. 510, June 1966, pages 173-185. Briefly, it comes that a 40 ml sample of the oil to be tested is cooled in a bath which is to be kept at about -34 resistant · ⁰ C. Periodically (at each ⁰ C drop in temperature starting from at least 2 ⁰ G above the cloud point) the cooled oil is tested by a fine mesh screen during prescribed time periods with respect to its flowability. The test apparatus consists of a pipette whose lower end is attached to a filter funnel, which in turn is located below the surface of the oil to be tested. Across the filter mouth, a 350-mesh screen with a defined area (12 mm in diameter) is stretched. The periodic tests are each initiated by drawing oil through the screen and up into the pipette to a 20-aml oil mark by applying a vacuum to the top of the pit. After each passage, the oil is returned immediately to the CFPP tube · The rest is at every degree Celsius

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Temperature drop repeated until that time at which the oil can not be drawn within 60 s in the pipette. The measured temperature is recorded as CFPP temperature

A further determination of the additive effect was carried out under the conditions of a slower, more natural cooling. The performance of these additives in the oils described was carried out by means of two variants of the pyrolysis sieve analysis (I ¹ SA) under different cooling conditions

, I ¹ SA 1

100 g samples of the fuel are cooled in the manner described below. The samples are shaken to homogenize the paraffin in the fuel suspension. 40 ml of this suspension are introduced into a pour point tube into which a 20 ml pipette with the lower end provided with a filter screen of about 1 cm diameter and below described mesh size is introduced. The paraffin-cloudy oil is then sucked through the filter sieve into the pipette with a suction pressure of 20 cm water column. »If the pipette fills in less than 30 s, the sample is considered to have passed, otherwise the analysis result is negative.

FSAJg

300 g samples of the fuel are cooled in the manner described below. Approximately 20 ml per sample are aspirated from the sample surface after cooling to prevent the test result from being affected by the abnormally large paraffin crystals forming on the surface when cooling. The sample quantity without surface crystals

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is then shaken for homogenization of the paraffin in the fuel suspension. A pipette with filter screen similar to that of PSA 1, which is also connected to a graduated cylinder (250 ml), is immersed in the sample and then all the oil is drawn through the sieve filter and pipette under a suction pressure of 30 cm sucked the measuring glass. The sample is considered enforced if all the oil has passed the filter sieve within 60 s.

Pipettes with mesh sieves of mesh numbers 20, 30, 40, 60, 80, 100, 120, 150, 200, 250, 350 are used to determine the smallest mesh size (corresponding to the highest mesh number) at which the mesh size Fuel can still be enforced ·

The cooling variants performed during the tests are summarized in the following table; the given letters are used in the following examples to describe the cooling preceding the actual fluidity test.

Cooling Cooling Start · End Temp. Cooling test rate (C / h> Temp., ⁰ C ⁰ C therefore, h

S 1.0 0 x) -11.5 36 T 1.0 0 -11.5 14 U 0 3 0 -11.5 36 V 1.0 1.5 - 8.5 0 cycle x) W 2.5 0 -11.5 60 X 1.0 0 -11.5 10 Y 0.3 0 -11.5 22 Z 1.0 0 -11.5 2 cycle

x) The tests marked "Cycle" were carried out by cooling the oil sample from the starting temperature in 1 C / h increments to the final temperature, held there for 30 hours, then warmed to starting temperature in 2 hours, where it was held again for 5 hours and finally cooled down again in 1 C / h increments.

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The examples below describe the performance of fuels containing various additive packages. Although each component could have been used as a solution in a low-reactant diluent, all numbers in Examples 1-5 are the actual additive concentrations in ppm of active substance.

EXAMPLE 1

The following results were obtained: Filterability test FSA 1 fuel 1

Additive (ppm)

^CTPP ° ^C

Flowable keitsver better (100) Carbon hydrogen polymer Polar connection (S) 30 (U) 30 -6 A2 (300) _ (S) 80 (U) 40 -19 A3 - - - (S) 40 (U) Failure - 10 20 (100) B1 (100) - (S) 60 (U) 120 -16 A2 (100) B1 (100) - (T) 80 (U) 40 -20 A1 (200) B1 (100) (T) 60 (U) 40 -16 A1 (100) - - (S) 150 (U) 120 -19 A2 (300) B1 (100) 01 (100) (S) 120 (U) 60 -14 A2 (100) - - (S) 250 (U) 150 -20 A1 B1 (100) 01 (100)

The letters in parentheses indicate the cooling method used ·

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EXAMPLE 2

With pilot fracture results obtained below 10% sample fraction Pilerability Test J ¹ SA 1 Cooling Condition V Fuel 1

Additive (ppm)

Passed mesh size

Flowable- Carbon-Polarity-Hydrogen- Improved Polymer

A2 (207) B1 (75) C1 (75) 30 A2 (69) B1 (75) C2 (75) 150 A2 (69) B1 (75) C3 (75) 60 A2 (69) 60

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EXAMPLE 3

Various hydrocarbon polymers were tested in combination with a flowability improver (A2) and a polar compound (G1).

The hydrocarbon polymer B2 had an average molecular weight of 60,000 to 65,000 and contained 44% by mass of ethylene. The hydrocarbon polymer B3 had an average molecular weight of 17,000 to 20,000 and contained 44% by mass of ethylene. Hydrocarbon polymer B 4 had an average molecular weight of about 55,000 and contained 67% by weight of ethylene.

The molecular masses had been measured by membrane osmometry; the polymers were prepared as essentially linearly configured using Ziegler-Natta catalysts.

Filterability Test PSA 1 Fuel 1

Additive (ppm) Passed mesh size

Fluent- Coal-polar cooling conditions

hydrogenation compound

better polymer W X Y Z

A2 (125) B2 - C1 _ 60 20 20 350 A2 (250) B1 - G1 120 40 40 200 A2 (175) B3 (75) 01 _ 350 60 60 150 A2 (175) B4 (75) G1 - 150 40 40 200 A2 (175) B2 (75) - 150 40 40 A2 (175) B1 (75) (100) 120 40 40 A2 (100) B3 (50) (100) 350 120 60 A2 (100) B4 (50) (100) 350 60 60 A2 (100) (50) (100) 350 40 40 A2 (100) (50) 350 40 40

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EXAMPLE 4

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By comparison, two low molecular weight hydrocarbon polymers - B5 and B6 - were tested in combination with fluidity improver A2.

Hydrocarbon polymer B5 had an average molecular weight of approximately 1500 and contained 89% by weight of ethylene and 11% by weight of propylene and had been prepared by a free radical synthesis.

Hydrocarbon polymer B6 was an ethylene homopolymer having an average molecular weight of about 1,000 (low density polyethylene).

Filterability Test FSA 2 Cooling Condition X Fuel 1

Additive (ppm) Passed mesh size

Flowable keitsver better Carbon hydrogen polymer B2 (50) 40 A2 (100) - B5 (50) 40 A2 (125) - B6 (50) 80 A2 (150) 120 A2 (100) 40 A2 (100) 40 A2 (100)

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EXAMPLE 5

Silidity Test PSA 2 Cooling Condition X Fuel 3

Additive (ppm) Passed mesh size

Flowable - hydrocarbon hydrogenated polymer

A2 (100) - 40

A2 (200) - 80

A2 (250) - 80

Δ2 (100) B2 (100) 80

A2 (200) B2 (50) 120

In this example, fuels containing a fluidity improver were compared with those fuels containing the fluidity improver and the hydrocarbon polymer.

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EXAMPLE 6

Various ethylene-propylene copolymers have been compiled to an additive-base combination for the flowability improvement of diesel oil and then tested in a middle distillate diesel oil having a cloud point of -12 ⁰ O · The additive basic combination (BAP) consisted of 20 mass% of a concentrate (about 55% by mass of high aromatic haphtha oil and about 45% by mass of distillate dilutability improver A2 described above), 20% by mass of sweat oil, 10% by mass of polar compound C4 and 50% by mass of heavy gasoline as a solvent

 These substances are described in more detail below.

Polar connection 04

This was a diamide of one mole of maleic anhydride and two moles of di / hydrogenated tallowamine.

to sweat

The sweat oil used here was produced as a distillation stream of an oil fraction in the boiling range of 370 to 522 ⁰ C - lying between the turbine lubricating oil flow and the paraffin cake containing residue. The sweat oil is a solid paraffin, contains 48.6% by weight of oil, has a density ( ⁰ API) of 0.8853 and an average molecular weight (gel permeation chromatography) of the non-oil portion of 484; 2.35 mass% of the n-paraffin content show a range of 19 to 28 (mainly 22 to 28) carbon atoms, the average number of carbon atoms is 24.9. With regard to the balance of the non-oil portion, iso and cycloparaffins of 23 to 39 carbon atoms were assumed.

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Aromatic heavy fuel (HAU)

This is a solvent for the additive packages, its aniline point is 24.6 ⁰ G, the density ( ⁰ API) is 0.933, the boiling range is between 179 and 235 ⁰ Oj the solvent is composed of 4 mass% paraffins, 6 , 7% by mass of naphthenes, 87.3 % by mass of aromatic compounds (eg polyalkylaromatics) and 2.0% by mass of olefins together.

The hydrocarbon polymer B7 consisted of an oil-diluted concentrate of about 5% by weight of an ethylene-propylene copolymer, which in turn consisted of about 44% by weight of ethylene and about 56% by weight of propylene having a thickening efficiency (TE) of 5 duration.

The thickening efficiency is the ratio of that mass% polyisobutylene (20,000 Staudinger molecular weight), the (es) required to thicken a Reference Oil to a viscosity of 12.4 centistokes at 210 ⁰ F to the mass% of ethylene-propylene -Copolymer, which are needed to thicken the reference oil to the same viscosity.

The reference oil LP Solvent 150N served - a weakly flowing solvent-refined Midcontinent hydrocarbon lubricating oil feedstock having a viscosity of 150 to 16O SUS at 100 ⁰ P, a viscosity index of 105 and a pour point at about 0 ⁰ F.

Based on a thickening efficiency of 5, the average molecular weight of the ethylene-propylene copolymer is estimated to be at least 100,000.

Hydrocarbon polymer B8 consisted of a polymer of about 44% by weight of ethylene and about 56% by weight of propylene,

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the thickening efficiency was 1.4, the average molecular weight ranged from about 17,000 to 20,000; The polymer was used at 13.6% by mass in an oil solution.

Hydrocarbon polymer B9 consisted of about 67% by weight of ethylene and about 23% by weight of propylene with a thickening efficiency of about 2.8 and an average molecular weight of about 55,000; the polymer was used dissolved in oil at 6.9 mass%.

The hydrocarbon polymer B10 consisted of an oil concentrate of about 3.4% by mass of hydrocarbon polymer B8 and 4.0% by mass of hydrocarbon polymer B10.

Hydrocarbon polymer B11 was an ethylene-propylene copolymer of about 44 mass% ethylene and about 56 mass% propylene with a thickening efficiency of about 2.8 and an average molecular weight of 60,000 to 65,000 applied with 8.3 mass% dissolved in oil.

Hydrocarbon polymer B12 consisted of a polyisobutylene having a thickening efficiency of 1 and a Staudinger molecular weight of about 18,000; it was dissolved with 20% by mass dissolved in oil. «

Hydrocarbon polymer B13 consisted of a polyisobutylene having a thickening efficiency of 0.6 and a Staudinger molecular weight of about 10,500; it was applied dissolved in oil at 35% by mass.

All of the above ethylene-propylene copolymers had been prepared by a Ziegler-Hatta synthesis

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an Mw / Mn ratio of less than 4. To determine the molecular masses of these essentially linear polymers, membrane osmometry was used.

The medium distilled diesel fuel was treated with either 2,000 ppm or 1,200 ppm (by weight based on the amount of diesel oil) of the base additive package (consisting of the ethylene-vinyl acetate copolymer, the sweat oil and the diamide); Further, varying amounts of the above-described hydrocarbon polymers B6 to B12 were added. The compositions thus obtained were tested in a cold flow test (LTPT) in the following manner:

200 cc of the treated oil composition are from ambient temperature to about 30 ⁰ F (-1 ⁰ C) cooled down, then with a rate of 2 ⁰ F (- 16 ° C / h) further to 0 ⁰ F (-18 ⁰ C) cooled and then filtered through a 17 micron mesh under 15.24 cm of mercury vacuum. The number of seconds required to pass the sample through the sieve, as well as the amount of substance passed through (in ml) are measured. If the sample was asserted in 60 or less seconds, then the test was considered fulfilled (P); if more than 60 seconds were required then the test was deemed not to be fulfilled (F).

The tested compositions and the test results are summarized in the table below.

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TABLE PPM ILTFT beio ⁰ P (- 18 ⁰ C) % Improvement additive Time, s P / P measured ml in BAP run 2 OOO BAP 36.7 P 195 - 2 000 BAP + 400 B7 33.7 P 195 8th 1 2 000 BAP + 400 B8 32.7 P 195 12 2 1 200 BAP 47.0 P 195 - 3 1 200 BAP + 400 B7 30.1 P 195 56 4 1 200 BAP + 400 B8 29.8 P 195 51 5 2 000 BAP + 400 B9 60.0 184.0 P P 135 195 - 68 6 1 200 BAP + 400 B10 56.9 P 195 - 18 7 1 200 BAP + 400 B11 35.8 P 195 31 8th 1 200 BAP + 400 B12 35.6 P 200 32 9 1 200 BAP + 400 B 13 36.8 P 200 27 10 1 200 BAP + 25 B11 60.0 100.0 P P 145 195 - 56 11 1 200 BAP + 25 B13 60.0 66.9 p. P 170 195 -30 · 12 800 A2 400 04 400 B7 46.5 P 190 13 500 A2 250 C4 400 B7 39.2 P 195 14 500 A2 400 B7 60, Oi ¹ P 0 - 15 800 petrolatum 60.0 400 B7 P 0 - 16 17

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As can be seen from the above table, the ethylene copolymers used in Runs 2 and 3 caused a shortening of the throughput time, the percentage improvement over the sole addition of the base additive pack (BAP) is 8 and 12 %. specified. In Run 4, the BAP level had been reduced to 1200 ppm. The low ethylene content of copolymers B7 and B8 of runs 5 and 6 caused significant increases in the flow rate of the treated oil through the fine screen. Run 7 shows that the use of the high ethylene polymer B9 exerted a thoroughly negative effect in two LTFT tests by extending the flow time of the oil through the sieve. Similar results can be seen in Run 8. Run 9 illustrates another example of the use of the low ethylene copolyester to increase the screen flow rate. "Runs 10 and 11 demonstrate the effectiveness of a polyisobutylene polymer. For Runs 12 and 13, the amount of polymer concentrate had been reduced to 25 ppm, which meant that only about 3 ppm active ingredient was actually added to the oil - based on active ingredient. Here, the added small amount of polymer caused an increase in the flow time through the filter and thus the failure of the test conditions, indicating that it needed at least in the composition under test a threshold amount of polymer to achieve satisfactory results.

Run 14 was treated with 88 ppm of the above-described oil concentrate of additive A2, 400 ppm of substance 04, and 400 ppm of the oil concentrate of hydrocarbon polymer B7. Run 15 had been charged with the same ingredients but in different proportions; in Run 16, only the diamide and the hydrocarbon polymer were used; Run 17 contained the flow

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Skill Concentrate A2 and Hydrocarbon Polymer B7; Finally, in Run 18, 800 parts of a petrolatum, namely, sweat oil, were used.

All of the hydrocarbon polymers B7 to B11 listed in the above table were used in the form of concentrates; in Run 2, for example, 400 ppm of the polymer B7 and 200 ppm of the actual copolymer were used.

Basically, the hydrocarbon polymers useful as lubricating oil viscosity index improvers of average molecular weights between 10 and 250,000 (such as B1 to B4 and B7 to B13) are particularly advantageously usable as B components.

Claims (8)

1.10.1982 226 87 0 2 58 478/18 Erfindunfisanapruch T * additive combination of substances of classes (A), (B) and (C), characterized in that (A) a distillate flow improving composition o j as defined above (E) a carbon monoxide polymer of average relative molecular weight
from derived version and relative molecular mass above 10 or one of these (C) a polar oil-soluble, different from (A) and (B) ο Compound 4 of the formula BX described herein ;;;.,>;:;::;atell; t * ^: "i ·; iv ''·;:':;·,; / el e. ·: Ui - .:: ^:;> L ·.) .O \ ^: "< · '/' An additive combination according to item 1, characterized in that the distillate flow enhancing composition is a distillate flow improving polymer having an average molecular weight in the range of 500 to 50,000 and provided with an oil-soluble ethylene base. An additive combination according to item 1 or 2, characterized in that said ethylene-base distillate fluidity improving polymer is a copolymer of from 4 to 20 molar proportions of ethylene per molar proportion of an unsaturated ester of the general formula 120KI198Ü.O4O2S 226870 2 - ΛΤ - 1.10 * 1982 58 478/18 where R _{1 is} methyl or hydrogen, R _{2 is} -OOCR, or -COOR ₄ and here again R _{4 is} a C ..- to Cpg-alkyl group and Ro is hydrogen or -COOR ₄ . 4 * Additive combination according to point 3 »characterized in that the polymer provided with an ethylene basic skeleton consists of an ethylene-vinyl acetate copolymer» 5 * Additive combination above the above points, characterized in that the hydrocarbon polymer is an olefin copolymer 6. Additive combination according to item 5 »characterized in that it is the hydrocarbon polymer is an ethylene-propylene copolymer. 7 * additive combination according to item 5 or 6, characterized in that the hydrocarbon polymer is a derived olefin copolymer of the type described above * 8. Additive combination according to the preceding points, characterized in that the polar oil-soluble compound consists of an oil-soluble nitrogen compound containing a total of at least 30 to 300 carbon atoms and having at least one straight-chain alkyl segment of 8 to 40 carbon atoms, the latter of which Class consisting of amino echelons and / or amides of hyrocarboxylic acids or anhydrides containing 1 to 4 carbonyl groups * 2 26 87 0 2 1.10.1982 58 478/18 9. additive combination according to item 8, characterized in that the mentioned nitrogen compound (0) consists of a phthalic acid or a phthalic anhydride whose two carboxylic acid groups reacted with secondary alkyl monoamide, the latter having alkyl groups having essentially 14 to 18 carbon atoms » 10. An additive concentrate, characterized in that it contains 30 to 80% by mass of a hydrocarbon diluent and 70 to 20% by mass of an additive combination according to one of the preceding points. 11 «Use of an additive combination, characterized in that it is used in a proportion of 0.001 to 0.5 percent by mass to improve the fluidity and Hltrierbarkeit a heating oil. Use according to item 11, characterized in that the additive combination contains one part by weight of the distillate flowability improver, 0.1 to 5 parts by mass of the hydrogen cyanide polymer and 0.2 to 10 parts by mass of the polar oil-soluble compound. 13. Use according to item 11 or 12, characterized in that the fuel oil is a middle distillate.